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The dimeric steroid SMR-3, featuring a 1,4-phenyldiboronic ester flanked by two pregnan-triol frameworks, was synthesized to explore the intramolecular dynamics of its central component. The structural data from single-crystal X-ray diffraction studies and the Hirshfeld analyses indicate small steric effects around the aromatic ring that should favor the intended motion. However, solid-state NMR data obtained through VT 13C{1H} CPMAS and 2H spin-echo experiments, using the deuterated analogue SMR-3D4, revealed that this component is rigid even at temperatures where other reported steroidal molecular rotors experience fast rotation (85 °C). A combination of classical molecular dynamics, molecular mechanics, and correlated ab initio calculations allowed us to distinguish the steric and electronic factors that restrict the potential motion in this compound. The experimental and computational data reveal that electronic components dominate the behavior and are responsible for the high rotational barrier in the SMR-3 crystal.
Assuntos
Imageamento por Ressonância Magnética , Simulação de Dinâmica Molecular , Rotação , Espectroscopia de Ressonância Magnética , EsteroidesRESUMO
The synthesis of four derivatives and the single-crystal X-ray structures of six 9-trifluoromethylxanthenediols (TFXdiols) I-VI are analyzed in this work. These compounds were obtained through superacid-catalyzed condensation of dihydroxybenzenes with 1,1,1-trifluoroacetone or 2,2,2-trifluoroacetophenone. The title molecules have a convex molecular structure due to their three fused rings of the xanthene moiety. We have found that, similar to resorcinol, the configuration of the hydroxyl groups is of great relevance for the crystal packing favoring either interactions above and below their molecular plane or lateral interactions that create layers. Considering that reports of TFXdiols are very scarce, our findings contribute to a better understanding of the molecular conformation and intermolecular interactions in their crystal structures. A similar analysis was extended to a fortuitous cocrystal obtained between 9-trifluoromethyl-9-(4'-fluorophenyl)-xanthenediol and 1,4-dihydroxybenzene, showing that these structures might be used to obtain cocrystals in the future.
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This work describes the synthesis and aggregation behavior of a dimeric bile acid derivative in which two steroid cores are bridged by a p-di(phenylethynyl)phenylene fluorophore. The studied compound contains three key characteristics: (a) restricted conformational equilibrium in solution, (b) efficient fluorescence conferred by the bridge, and (c) medium responsiveness encoded in the steroid fragments. The incorporation of the three components afforded a compound that generates nano- and micrometric spherical particles with aggregation-responsive fluorescence emission. The observed self-assembly process of the featured molecule was induced by the gradual addition of water to the tetrahydrofuran (THF) solution. This aggregation led to significant changes in fluorescence that went from two bands at λem values of 370 and 390 nm in pure THF to a new spectrum with two maxima at λem values of 395 and 418 nm at high water contents, without a decrease in emission. The observed changes can be ascribed to weakly coupled aggregation, a hypothesis supported by multiscale molecular modeling, which sheds light on the mechanism of the self-assembly of this unconventional amphiphile.
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Ácidos e Sais Biliares , Polímeros , Modelos Moleculares , Espectrometria de Fluorescência , ÁguaRESUMO
Hydrolysis reactions of di- and trinuclear organotin halides yielded large novel cage compounds containing Sn-O-Sn bridges. The molecular structures of two octanuclear tetraorganodistannoxanes showing double-ladder motifs, viz., [{Me3 SiCH2 (Cl)SnCH2 YCH2 Sn(OH)CH2 SiMe3 }2 (µ-O)2 ]2 [1, Y=p-(Me)2 SiC6 H4 -C6 H4 Si(Me)2 ] and [{Me3 SiCH2 (I)SnCH2 YCH2 Sn(OH)CH2 SiMe3 }2 (µ-O)2 ]2 â 0.48 I2 [2â 0.48 I2 , Y=p-(Me)2 SiC6 H4 -C6 H4 Si(Me)2 ], and the hexanuclear cage-compound 1,3,6-C6 H3 (p-C6 H4 Si(Me)2 CH2 Sn(R)2 OSn(R)2 CH2 Si(Me)2 C6 H4 -p)3 C6 H3 -1,3,6 (3, R=CH2 SiMe3 ) are reported. Of these, the co-crystal 2â 0.48 I2 exhibits the largest spacing of 16.7â Å reported to date for distannoxane-based double ladders. DFT calculations for the hexanuclear cage and a related octanuclear congener accompany the experimental work.
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We demonstrate here that the Ugi-Sonogashira protocol can be successfully used to obtain five new molecular rotors 10a-e with strong emission. They have been synthesized by combining multicomponent Ugi stators and several aromatic rotary components: phenylene, p-xylene, naphthalene and anthracene. The synthesized conjugated rotors are highly fluorescent (Φf = 0.39 to Φf = 0.10), and changes in their emission were observed upon variations of the surrounding media. Particularly, we found that they are sensitive to aggregation (THF/water) or high viscosity (methanol/glycerol) conditions. This work paves the way to develop new emissive rotors with exciting photophysical properties.
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A series of hybrid dimers having orthogonal steroidal cores bridged by a chroman ketal moiety were obtained by Pd-catalyzed three-component reactions of steroid alkynols, 2-formylestradiol 17-monoacetate, and methyl orthoformate, via ortho-quinone methide intermediates. One of the obtained L-shaped scaffolds showed an inefficient crystal packing featuring large channels within the crystal array. Monte Carlo simulations indicate that these voids preferentially allocate n-hexane, opening the way to explore further applications of similar organic crystalline materials as selective hosts for small molecules.
Assuntos
Indolquinonas , Paládio , Catálise , EsteroidesRESUMO
Two diastereomeric crystalline steroid dimers were obtained by acid-catalyzed double acetalization of (20S)-5α-pregnan-3ß,16ß,20-triol 3-monoacetate with terephtalaldehyde. These compounds were characterized by NMR in solution, MS, single-crystal X-ray diffraction, and variable-temperature solid-state NMR by 13C cross-polarization magic angle spinning (CPMAS). While the phenylene rotator in the SR diastereomer remains static even at 373 K, the RR isomer shows a slow rotational process of the phenylene ring at temperatures above room temperature and thus may be considered the first crystalline steroid molecular rotor without the alkyne axle.
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Two new crystalline rotors 1 and 2 assembled through N-Hâ â â N hydrogen bonds by using halogenated carbazole as stators and 1,4-diaza[2.2.2]bicyclooctane (DABCO) as the rotator, are described. The dynamic characterization through 1 H T1 relaxometry experiments indicate very low rotational activation barriers (Ea ) of 0.67â kcal mol-1 for 1 and 0.26â kcal mol-1 for 2, indicating that DABCO can reach a THz frequency at room temperature in the latter. These Ea values are supported by solid-state density functional theory computations. Interestingly, both supramolecular rotors show a phase transition between 298 and 250â K, revealed by differential scanning calorimetry and single-crystal X-ray diffraction. The subtle changes in the crystalline environment of these rotors that can alter the motion of an almost barrierless DABCO are discussed here.
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Crystal adaptronics is an emergent materials science discipline at the intersection of solid-state chemistry and mechanical engineering that explores the dynamic nature of mechanically reconfigurable, motile, and explosive crystals. Adaptive molecular crystals bring to materials science a qualitatively new set of properties that associate long-range structural order with softness and mechanical compliance. However, the full potential of this class of materials remains underexplored and they have not been considered as materials of choice in an engineer's toolbox. A set of general performance metrics that can be used for quantification of the performance of these prospective dynamic materials as micro- and macroactuators is presented. The indices are calculated on two selected representatives of thermosalient solids-materials that undergo rapid martensitic transitions accompanied with macroscopic locomotion. Benchmarking of their performance against extensive set of data for the existing actuator classes and visualization using materials property charts uncover the hidden potential and advantages of dynamic crystals, while they also reveal their drawbacks for actual application as actuators. Altogether the results indicate that, if the challenges with fabrication and implementation in devices are overcome, adaptive molecular crystals can have far-reaching implications for emerging fields such as smart microelectronics and soft microrobotics.
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Amphidynamic motion in metal-organic frameworks (MOFs) is an intriguing emergent property, characterized by high rotational motion of the phenylene rings that are embedded within an open, rigid framework. Here, we show how the phenylene rings in the organic linkers of the water stable MOF PEPEP-PIZOF-2 exhibit multiple rotational rates as a result of the electronic structure of the linker, with and without the presence of highly interacting molecular guests. By selective 2H enrichment, we prepared isotopologues PIZOF-2d4 and PIZOF-2d8 and utilized solid-state 13C and 2H NMR to differentiate the dynamic behavior of specific phenylenes in the linker at room temperature. A difference of at least one order of magnitude was observed between the rates of rotation of the central and outer rings at room temperature, with the central phenylene ring, surrounded by ethynyl groups, undergoing ultrafast 180° jumps with frequencies higher than 10 MHz. Moreover, loading tetracyanoquinodimethane (TCNQ) within the pores produced significant changes in the MOF's electronic structure, but very small changes were observed in the rotational rates, providing an unprecedented insight into the effects that internal dynamics have on guest diffusion. These findings would help elucidate the in-pore guest dynamics that affect transport phenomena in these highly used MOFs.
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This work describes the use of C-Hâ¯F-C contacts in the solid-state from the stator towards the rotator to fine-tune their internal motion, by constructing a set of interactions that generate close-fitting cavities in three supramolecular rotors 1-3I. The crystal structures of these rotors, determined by synchrotron radiation experiments at different temperatures, show the presence of such C-Hâ¯F-C contacts between extended carbazole stators featuring fluorinated phenyl rings and the 1,4-diazabicyclo[2.2.2]octane (DABCO) rotator. According to the 2H NMR results, using deuterated samples, and periodic density functional theory computations, the rotators experience fast angular displacements (preferentially 120° jumps) due to their low rotational activation energies (E a = 0.8-2.0 kcal mol-1). The higher rotational barrier for 1 (2.0 kcal mol-1) is associated with a larger number of weak C-Hâ¯F-C contacts generated by the stators. This strategy offers the possibility to explore the correlation among weak intermolecular forces, cavity shape, and internal dynamics, which has strong implications in the design of future fine-tuned amphidynamic crystals.
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A multicomponent diversity-oriented synthesis of new highly emissive tetracyclic isoquinolines that target specific organelles is described. The title compounds were prepared via a three-step protocol starting with an Ugi four-component reaction, followed by either an intramolecular alkyne hydroarylation and subsequent alkene isomerization or through a Pomeranz-Fritsch-type cyclization with a final intramolecular Heck reaction. Subcellular localization studies of these compounds using green channel confocal microscopy revealed remarkable and distinctive distribution patterns in live cells, showing an unprecedented high selectivity and imaging contrast. The differentiated organelle visualization-including localizers for mitochondria, lysosomes, Golgi apparatus, endoplasmic reticulum, and plasma membrane-was achieved by varying the nature of the tetracyclic system and substituent pattern, changing the original four-component set in the starting Ugi reaction.
Assuntos
Corantes Fluorescentes/química , Isoquinolinas/síntese química , Isoquinolinas/metabolismo , Frações Subcelulares/metabolismo , Células HeLa , Humanos , Isoquinolinas/químicaRESUMO
A new rotor exhibits rich solvatomorphism behavior with eight X-ray structures obtained. A heterogeneous solid obtained by mechanical stress exhibited a dominant isotropic 2H line shape at high temperatures. The motion occurs only in the amorphous component of this solid, with an Ea of 7.4 kcal mol-1 and a low pre-exponential factor A of 6.22 × 1010 s-1, which indicates that the motion requires the distortion of the molecular axis.
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Herein we report two crystalline molecular rotors 1 and 4 that show extremely narrow signals in deuterium solid-state NMR spectroscopy. Although this line shape is typically associated with fast-moving molecular components, our VT 2H NMR experiments, along with X-ray diffraction analyses and periodic DFT computations show that this spectroscopic feature can also be originated from low-frequency intramolecular rotations of the central phenylene with a cone angle of 54.7° that is attained by the cooperative motion of the entire structure that distorts the molecular axis to rotation. In contrast, two isomeric structures (2 and 3) do not show a noticeable intramolecular rotation, because their crystallographic arrays showed very restricting close contacts. Our findings clearly indicate that the multiple components and phase transitions in crystalline molecular machines can work in concert to achieve the desired motion.
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Crystals of molecular rotor 1 with a central 1,4-phenylene rotator linked to two molecules of the steroid mestranol were prepared with 1%, 5%, 20%, and up to 40% of the analogous 2, which contains a larger 2,3-difluorophenylene rotator and effectively acts as a monkey wrench that affects the rotation of the host. The packing motif of the desired P32 crystal form consists of 1D columns of nested rotors arranged in helical arrays with the central aromatic rotators disordered over two sites related by 85° rotation about their 1,4-axes. Rotational dynamics measured by quadrupolar echo 2H NMR line shape analysis were analyzed in terms of a process model that involves degenerate 180° jumps in the fast exchange regime combined with a highly correlated and entropically demanding jump of 85° between the two dynamically disordered sites. While the enthalpic and entropic barriers for the 180° jump estimated from 2H T1 measurements were Δ H⧧ = 2.7 ± 0.1 kcal mol-1 and Δ S⧧ = -5.0 ± 0.5 cal mol-1 K-1, respectively, the corresponding parameters for the slower 85° jumps, determined by line shape analysis, were Δ H⧧ = 2.2 kcal mol-1 and Δ S⧧ = -23 cal mol-1 K-1. Increasing amounts of the larger molecular rotor 2 in the solid solution results in significant dynamic perturbations as the guest, acting as a monkey wrench, reaches values of one out of every five molecular rotors in the chain.
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A novel steroid molecular rotor was obtained in four steps from the naturally occurring spirostane sapogenin diosgenin. The structural and dynamic characterization was carried out by solution NMR, VT X-ray diffraction, solid state 13C CPMAS, and solid state 2H NMR experiments. They allowed the identification of a fast dynamic process with a frequency of 14 MHz at room temperature, featuring a barrier to rotation Ea = 7.87 kcal mol-1. The gathered experimental evidence indicated the presence of a hydrogen bond that becomes stronger as the temperature lowers. This interaction was characterized using theoretical calculations, based on topological analyses of the electronic density and energies. In addition, combining theoretical calculations with experimental measurements, it was possible to propose a partition to Ea (â¼8 kcal/mol) into three contributions, that are the cost of the intrinsic rotation (â¼2 kcal/mol), the hydrogen bond interaction (â¼2 kcal/mol), and the packing effects (â¼2-3 kcal/mol). The findings from the present work highlight the relevance of the individual components in the function of molecular machines in the solid state.
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The use of the multicomponent Ugi reaction to rapidly prepare a library of dumbbell-like molecular rotors is highlighted here. The synthetic strategy consisted of the atom-economic access to 15 bulky and structurally diverse iodinated stators, which were cross-coupled to the 1,4-diethynylphenylene rotator. From those experiments, up to six rotors 1a-c and 1l-n were obtained, with yields ranging from 35 to 69% per coupled C-C bond. In addition to the framework diversity, five of these compounds showed aggregate-enhanced emission properties thanks to their conjugated 1,4-bis(phenylethynyl)benzene cores, a property that rises by increasing the water fraction (fw) in their THF solutions. The results highlight the significance of the diversity-oriented synthesis of rapid access to new molecular fluorescent rotors.
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We report for the first time the high sorption properties of a molecular rotor with no permanent voids or channels in its crystal structure. Such crystalline phase originates from THF, DCM, or the irreversible desolvation of entrapped benzene molecules. From these, the benzene in its solvate form acts as rotation stopper, as supported by dynamic characterization using solid-state 2H NMR experiments. In the solvent-free form, the diffusion of small quantities of iodine vapors caused a significant change in the intramolecular rotation, increasing the known activation energy to rotation from 8.5 to 10.6 kcal mol-1. Notably, those results paved the way for the discovery of the high CO2 uptake (201.6 cm3 g-1 at 196 K, under 1 atm) and acetone (5 wt %), a sorption property that was attributed to both, the restriction of the molecular rotation at low temperatures and the flexibility of the molecular axle made of conjugated p-(ethynylphenylene), surrounded by carbazole.
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Liquid-like dynamics of a covalent 1,4-phenylene rotator have been unveiled in 1 with a brominated stator showing type-II halogen bonds. This singular rotation is favored by synergistic molecular changes in stacked molecules, according to VT solid state NMR, 1H T1 relaxometry and VT X-ray experiments of this highly crystalline compound.
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A molecular rotor built with a stator formed by two rigid 9ß-mestranol units having a 90° bent angle linked to a central phenylene rotator has an ideal structure to examine aromatic CH/π interactions. Energies and populations of the multiple solution conformations from quantum-mechanical calculations and molecular dynamics simulations were combined with variable-temperature (VT) (1)H NMR data to establish the enthalpy of this interaction and the entropy associated with rotation about a single bond. Rotational dynamics in the solid state were determined via VT cross-polarization magic-angle spinning (13)C NMR spectroscopy.